CN114446667A - Preparation method of high-dielectric-constant electrode foil - Google Patents
Preparation method of high-dielectric-constant electrode foil Download PDFInfo
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- CN114446667A CN114446667A CN202210047048.2A CN202210047048A CN114446667A CN 114446667 A CN114446667 A CN 114446667A CN 202210047048 A CN202210047048 A CN 202210047048A CN 114446667 A CN114446667 A CN 114446667A
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- electrode foil
- foil
- titanium dioxide
- constant electrode
- aqueous solution
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/04—Drying; Impregnating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of capacitor manufacturing, and discloses a preparation method of a high-dielectric-constant electrode foil, which comprises the following steps: soaking the etched foil in an aqueous solution of ammonium fluotitanate, generating a titanium dioxide oxide layer with the thickness less than or equal to 1.0nm on the surface of the etched foil through parameter regulation and control in the soaking process, forming a thin aluminum oxide layer on the titanium dioxide oxide layer through pre-formation, and then soaking the aluminum oxide layer in the aqueous solution of ammonium fluotitanate to generate a new titanium dioxide oxide layer. The composite film layer obtained by the method not only effectively improves the content of titanium dioxide in the composite film, but also does not increase leakage current due to overlarge crystalline particles. Compared with a general formation process, the capacity of the high-dielectric-constant aluminum electrode foil prepared by the method disclosed by the invention is improved by 15-30%.
Description
Technical Field
The invention relates to the technical field of capacitor manufacturing, in particular to a preparation method of a high-dielectric-constant electrode foil.
Background
With the increasing requirements of miniaturization and light weight of electronic devices, higher requirements are also put forward on the capacity of the aluminum electrolytic capacitor. The aluminum electrode foil is used as a core component of the aluminum electrolytic capacitor and plays a decisive role in the capacity of the capacitor. In recent years, more and more researches are focused on doping a valve metal oxide having a high dielectric constant into an aluminum oxide layer of an electrode foil to increase the overall dielectric constant of the electrode foil, thereby achieving the purpose of increasing the capacity.
Common chemical methods for preparing composite oxide films include electrochemical deposition, sol-gel (sol-gel), and hydrolytic deposition. The electrochemical deposition method needs to consume electric energy in the production process, has expensive equipment and higher cost, and is not suitable for batch production. Both the sol-gel method and the hydrolysis deposition method deposit a valve metal precursor on the surface of the etched foil by soaking, and then obtain a valve metal oxide by high-temperature heat treatment. The difference is that the sol-gel method is an organic system, organic solvent is introduced in the production process, the subsequent treatment is difficult, the environment is polluted, and the sol-gel system is unstable. The hydrolysis deposition method is an aqueous solution system and is free from contamination, and a method of obtaining titanium dioxide having a high dielectric constant by hydrolysis of ammonium fluorotitanate is proposed in the patent "electrode foil for electronic container (TW 200644012A)", but the content of the deposited valve metal is small and the increase of the specific volume is limited.
Disclosure of Invention
In order to solve the problems and overcome the defects in the prior art, the invention is realized by the following technical scheme: the method is innovatively improved on the conventional hydrolysis deposition method, because the content of titanium dioxide obtained by one-time soaking is low, but the soaking time is too long, the crystal particles of the titanium dioxide are increased, the defects of a finally formed composite film are more, and the leakage current of the product is high. Therefore, the thickness of the titanium dioxide oxide film obtained by one-time soaking is controlled to be less than 1.0nm, and the total content of the titanium dioxide is increased by soaking the pretreatment liquid again after the pre-formation.
The invention is realized by the following technical scheme: a preparation method of a high dielectric constant electrode foil mainly comprises the following steps:
step 1, soaking a corrosion foil in an ammonium fluotitanate (NH4)2TiF6 aqueous solution, controlling the reaction temperature at 20-50 ℃ for 3-10 min, taking out, washing with pure water, drying, placing in a 200-400 ℃ muffle furnace, preserving heat for 2-5 min, carrying out annealing heat treatment, and corroding the surface of the foil to generate a titanium dioxide crystal film;
step 2, placing the corrosion foil treated in the step 1 in an ammonium adipate electrolyte, and performing pre-formation under a certain anodic oxidation voltage to generate a thin composite oxide film;
step 3, soaking the etched foil treated in the step 2 in an ammonium fluotitanate aqueous solution, controlling the reaction temperature at 40-80 ℃ for 3-10 min, taking out, washing with pure water, drying, placing in a muffle furnace at 300-600 ℃ for heat preservation for 2-5 min, and carrying out annealing heat treatment to generate a new titanium dioxide crystalline layer;
and 4, carrying out conventional anodic oxidation formation treatment on the etched foil treated in the step 3 in an electrolyte solution to obtain the high-dielectric-constant electrode foil.
Further, in the step 1, the concentration of the aqueous solution of ammonium fluotitanate (NH4)2TiF6 is 0.01-0.5 mol/L.
Furthermore, in the step 1, the thickness of the generated titanium dioxide crystal film is less than or equal to 1.0 nm.
Further, in the step 2, the concentration of the ammonium adipate electrolyte is 7-15%.
Further, in the step 2, the predetermined anodic oxidation voltage is 0.02 to 0.1 times of the final withstand voltage of the electrode foil.
Further, in the step 3, the concentration of the aqueous solution of ammonium fluotitanate (NH4)2TiF6 is 0.5 to 1.0 mol/L.
Further, in the step 1, the thickness of the titanium dioxide crystal film to be formed is one of 1.0nm, 0.8nm, 0.6nm and 0.4 nm.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a high-dielectric-constant electrode foil, which is characterized in that a high-dielectric-constant layer is obtained by utilizing an improved hydrolytic deposition method, the thickness of a titanium dioxide oxide film obtained by primary soaking is controlled to be below 1.0nm, the total content of titanium dioxide is increased by secondary soaking, and a composite oxide film is obtained after formation.
Compared with the prior art, the specific volume of the aluminum electrolytic capacitor manufactured by the method disclosed by the invention is improved by 15-30%, and the leakage current is not influenced. The method is simple and convenient to operate, low in cost, free of organic solvent and environment-friendly, and the prepared composite oxide film is high in uniformity and consistency and can be linked with industrial large-scale production.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more easily understand the advantages and features of the present invention, and to clearly and clearly define the scope of the present invention.
Example (b):
step 1, soaking a corrosion foil in an ammonium fluotitanate aqueous solution with the concentration of 0.05mol/L, controlling the reaction temperature at 25 ℃ for 3min, taking out the corrosion foil, washing the corrosion foil with pure water, airing the corrosion foil, placing the corrosion foil in a muffle furnace at 200-400 ℃ for heat preservation for 3min, and carrying out annealing heat treatment to generate a titanium dioxide crystal film on the surface of the corrosion foil, wherein the thickness of the titanium dioxide crystal film is 1.0 nm;
step 2, placing the corrosion foil processed in the step 1 in 10% ammonium adipate electrolyte, and performing pre-formation under an anodic oxidation voltage of 5V to generate a thin composite oxide film;
step 3, soaking the etched foil treated in the step 2 in 0.25mol/L ammonium fluotitanate aqueous solution, controlling the reaction temperature at 50 ℃ for 3min, taking out, washing with pure water, drying, placing in a muffle furnace at 300-600 ℃ for 3min, and carrying out annealing heat treatment to generate a new titanium dioxide crystalline layer;
and 4, carrying out conventional anodizing formation treatment on the etched foil treated in the step 3 in an electrolyte solution at 60Vf to obtain the high-dielectric-constant electrode foil.
Comparative example:
the same etched foil as in example was used, and only the conventional anodizing formation treatment method as in example step (4) was used, and the formation voltage was 60Vf, to obtain a common electrode foil of comparative example.
The comparison table of the performance parameters of the low-leakage low-voltage electrode foil prepared in the example and the electrode foil prepared by the original process is as follows:
by using the technical scheme disclosed by the application, the comparison result of the performance parameters of the prepared aluminum electrode foil and the electrode foil prepared by the existing process (namely the scheme given by the comparative example) is shown in the table, and as can be seen from the table, the technical scheme disclosed by the embodiment of the application can effectively improve the specific volume of the electrode foil.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. The preparation method of the high dielectric constant electrode foil is characterized by mainly comprising the following steps:
step 1, soaking the etched foil in ammonium fluotitanate (NH)4)2TiF6In the aqueous solution, controlling the reaction temperature at 20-50 ℃ for 3-10 min, taking out, washing with pure water, drying, placing in a muffle furnace at 200-400 ℃ for heat preservation for 2-5 min, carrying out annealing heat treatment, and corroding the surface of a foil to generate a titanium dioxide crystalline film;
step 2, placing the corrosion foil processed in the step 1 in an ammonium adipate electrolyte, and performing pre-formation at a certain anodic oxidation voltage to generate a thin composite oxide film;
step 3, soaking the etched foil treated in the step 2 in an ammonium fluotitanate aqueous solution, controlling the reaction temperature at 40-80 ℃ for 3-10 min, taking out, washing with pure water, drying, placing in a muffle furnace at 300-600 ℃ for heat preservation for 2-5 min, and carrying out annealing heat treatment to generate a new titanium dioxide crystalline layer;
and 4, carrying out conventional anodic oxidation formation treatment on the etched foil treated in the step 3 in an electrolyte solution to obtain the high-dielectric-constant electrode foil.
2. The method for preparing a high dielectric constant electrode foil as claimed in claim 1, wherein in the step 1, ammonium fluorotitanate (NH) is used4)2TiF6The concentration of the aqueous solution is 0.01-0.5 mol/L.
3. The method for preparing a high dielectric constant electrode foil as claimed in claim 1, wherein the thickness of the titanium dioxide crystal film formed in step 1 is less than or equal to 1.0 nm.
4. The method for preparing the high-dielectric-constant electrode foil as claimed in claim 1, wherein in the step 2, the concentration of the ammonium adipate electrolyte is 7% -15%.
5. The method for preparing a high dielectric constant electrode foil as claimed in claim 1, wherein the certain anodic oxidation voltage in step 2 is 0.02 to 0.1 times of the final withstand voltage of the electrode foil.
6. The method for preparing a high dielectric constant electrode foil as claimed in claim 1, wherein in the step 3, ammonium fluorotitanate (NH) is used4)2TiF6The concentration of the aqueous solution is 0.5-1.0 mol/L.
7. The method for preparing a high dielectric constant electrode foil as claimed in claim 1, wherein the thickness of the titanium dioxide crystal film formed in step 1 is one of 1.0nm, 0.8nm, 0.6nm and 0.4 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210047048.2A CN114446667B (en) | 2022-01-17 | 2022-01-17 | Preparation method of high dielectric constant electrode foil |
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| CN202210047048.2A CN114446667B (en) | 2022-01-17 | 2022-01-17 | Preparation method of high dielectric constant electrode foil |
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| CN114446667A true CN114446667A (en) | 2022-05-06 |
| CN114446667B CN114446667B (en) | 2023-09-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116092834A (en) * | 2023-03-31 | 2023-05-09 | 南通海星电子股份有限公司 | High-specific capacitance electrode foil and preparation method thereof |
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| WO2006008970A1 (en) * | 2004-07-23 | 2006-01-26 | Nippon Steel Corporation | Electrode foil for capacitor and method for producing same |
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| WO2006117985A1 (en) * | 2005-04-27 | 2006-11-09 | Nippon Steel Corporation | Electrode foil for capacitor |
| JP2006310494A (en) * | 2005-04-27 | 2006-11-09 | Nippon Steel Corp | Electrode foil for capacitor |
| JP2006310493A (en) * | 2005-04-27 | 2006-11-09 | Nippon Steel Corp | Electrode foil for capacitor |
| JP2008172186A (en) * | 2006-03-29 | 2008-07-24 | Matsushita Electric Ind Co Ltd | Manufacturing method of electrode foil |
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| JP2013004650A (en) * | 2011-06-15 | 2013-01-07 | Panasonic Corp | Anode foil for electrolytic capacitor and aluminum electrolytic capacitor using the same or functional polymer aluminum electrolytic capacitor and manufacturing method of anode foil for electrolytic capacitor |
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- 2022-01-17 CN CN202210047048.2A patent/CN114446667B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006008970A1 (en) * | 2004-07-23 | 2006-01-26 | Nippon Steel Corporation | Electrode foil for capacitor and method for producing same |
| WO2006117985A1 (en) * | 2005-04-27 | 2006-11-09 | Nippon Steel Corporation | Electrode foil for capacitor |
| JP2006310494A (en) * | 2005-04-27 | 2006-11-09 | Nippon Steel Corp | Electrode foil for capacitor |
| JP2006310493A (en) * | 2005-04-27 | 2006-11-09 | Nippon Steel Corp | Electrode foil for capacitor |
| CN1766168A (en) * | 2005-10-10 | 2006-05-03 | 西安交通大学 | Titanium oxide/aluminum oxide high dielectric constant composite anode film preparation method |
| JP2008172186A (en) * | 2006-03-29 | 2008-07-24 | Matsushita Electric Ind Co Ltd | Manufacturing method of electrode foil |
| CN101651046A (en) * | 2009-07-22 | 2010-02-17 | 电子科技大学 | Preparation method of Al2O3/TiO2 compound dielectric film aluminum electrode foil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116092834A (en) * | 2023-03-31 | 2023-05-09 | 南通海星电子股份有限公司 | High-specific capacitance electrode foil and preparation method thereof |
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